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题名: Photodissociation dynamics of D2O via the (B)over-tilde((1)A(1)) electronic state
作者: Cheng, Yuan1;  Cheng, Lina1;  Guo, Qing1;  Yuan, Kaijun1;  Dai, Dongxu1;  Yang, Xueming1
刊名: JOURNAL OF CHEMICAL PHYSICS
发表日期: 2011-03-14
DOI: 10.1063/1.3555589
卷: 134, 期:10
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Physics, Atomic, Molecular & Chemical
研究领域[WOS]: Physics
英文摘要: Photodissociation dynamics of D2O in the (B) over tilde((1)A(1)) state at different photolysis wavelengths have been investigated using the D-atom Rydberg "tagging" time-of-flight (TOF) technique, in combination with a tunable vacuum ultraviolet photolysis light source. TOF spectra of the D-atom product from the D2O photodissociation in both parallel and perpendicular polarizations have been measured. Product kinetic energy distributions and angular distributions have been derived from these TOF spectra. From these distributions, internal state distributions of the OD product as well as the OD quantum state specific angular anisotropy parameters have been derived. Two product channels governed by distinct dissociation dynamics have been clearly observed in the (B) over tilde((1)A(1)) state photodissociation: ground electronic state radical product OD(X (2) Pi) + D and excited electronic state OD(A (2) Sigma(+)) + D. The OD(A) + D channel proceeds via adiabatic pathway on the (B) over tilde((1)A(1)) state surface, producing rovibrational excitation in the OD(A) product, while the OD(X) + D channel is generated through nonadiabatic pathway mainly via conical intersections between the (B) over tilde((1)A(1)) and the (X) over tilde((1)A(1)) state surfaces. Due to strong angular force induced by the conical intersections, the OD(X) product is extremely hot in the rotational excitation close to the energy limit (N similar to 50 for v = 0). However, the vibrational excitation is cold in the OD(X) product with dominant population in the ground vibrational state v = 0. Detailed experimental results at different photolysis wavelengths show that at higher energy the unstable periodic orbit, from which dissociation starts, on the (B) over tilde state has stronger excitation degree of the OD internal state. The negative angular anisotropy parameters of the OD(A) products suggest that the angular forces in this adiabatic dissociation pathway from these periodic orbits have changed the original angular distribution of the D2O molecule excited by the (B) over tilde((1)A(1)) <- (X) over tilde((1)A(1)) parallel transition. (C) 2011 American Institute of Physics. [doi:10.1063/1.3555589]
关键词[WOS]: MULTIPHOTON IONIZATION SPECTROSCOPY ;  DIFFUSE VIBRATIONAL-STRUCTURES ;  2ND ABSORPTION-BAND ;  OH PROMPT EMISSION ;  ALPHA 121.6 NM ;  DISSOCIATION DYNAMICS ;  PREDISSOCIATION-DYNAMICS ;  (D)OVER-TILDE STATES ;  VACUUM-ULTRAVIOLET ;  RYDBERG STATES
语种: 英语
WOS记录号: WOS:000288395400017
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142427
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China

Recommended Citation:
Cheng, Yuan,Cheng, Lina,Guo, Qing,et al. Photodissociation dynamics of D2O via the (B)over-tilde((1)A(1)) electronic state[J]. JOURNAL OF CHEMICAL PHYSICS,2011,134(10).
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